Methylol amide adduct sizing composition



United States Patent Ofiice 3,321,324 Patented May 23, 1967 3,321,324 METHYLGL AMIDE ADDUCT SIZING COMPOSITION Roy H. Boggs, Greenville, S.C., and George W. Cogswell, Decatur, 11]., assignors to A. E. Staley Manufacturing Company, Decatur, 11]., a corporation of Delaware No Drawing. Filed June 20, 1963, Ser. No. 289,386

13 Claims. (Cl. 106-211) This invention relates to a new warp sizing agent for textile yarns, which comprises a methylol amide of an adduct of a maleyl compound and an ethylenically unsaturated fatty acid ester of a polyhydric alcohol.

In the production of textile materials, it is necessary to apply a coating or size to the fibers to protect them from abrasion during the various operations involved in the formation of the cloth. The coating or size must be flexible, tough and normally capable of removal by conventional desizing techniques. The flexibility and toughness are obvious necessities since the fibers, threads or filaments are twisted and bent in various directions and rub against the loom parts. In general, the size must be readily soluble in an aqueous system (dilute aqueous alkali, for example) or else readily digestible by appropriate enzyme desizing agents. Glass fibers can be des'ized by burning the size off, provided the burnt oif size yields a light colored or preferably white ash. In some cases, it is desirable to use a warp sizing agent which forms a permanent uniform size on the finished textile product.

In the case of the so-called hydrophilic fibers, such as cotton, the most commonly used warp sizing agent is starch. This natural polymer is used in many forms, such as the hydrolyzed starches, the dextrins, and the partially etherified or esterified starches. Also, in the case of cotton, such polymers as water-soluble carboxymethyl cellulose, water-soluble hydroxyethyl cellulose and the various natural gums (guar gum, gum arabic, sodium alginate, etc.) have been used.

These warp sizing agents offer little protection to yarn prepared from the so-called hydrophobic fibers, such as nylon, polyesters (polyethylene terephthalate), polyacrylonitrile, cellulose esters (cellulose acetate), fiber glass, etc. This is because the applied coatings do not adhere tenaciously to the hydrophobic fiber and are therefore scraped away by abrasion.

A large number of synthetic fiber sizing agents, which are either water-soluble or dilute alkali-soluble, have been employed to size these hydrophobic fibers with variable success. However, these fiber sizing agents, which include, polyacrylic acid, partially hydrolyzed polymers of acrylonitrile and/ or lower alkyl acrylate, maleic anhydride copolymers, maleic acid half-ester copolymers, polyvinyl alcohol, etc., are considerably more expensive than the natural polymeric sizes based on starch and cellulose.

Even in the case of the yarns of hydrophilic fibers, starch warp sizing agents do not have as high a degree of film clarity, tensile strength, and abrasion resistance that one might desire. However, starch is by far the least exmnsive sizing agent available.

The principal object of this invention is to provide a new low-cost warp sizing agent, which can be used alone, or together with other warp sizing agents as a size for hydrophobic yarns or hydrophilic yarns. Another object of this invention is to provide a warp sizing material, which serves to bind natural polymers, particularly starch, to hydrophobic fibers. Another object of this invention is to provide a warp sizing agent, which improves the size clarity, tensile strength and abrasion resistance of yarns sized with starch warp sizing agents and which inhibits the growth of molds in starch warp sizing pastes.

We have now found that aqueous dispersions of methylol amides of adducts formed between alpha, betaethylenically unsaturated dicarboxy compounds (maleyl compounds) and polyhydric alcohol esters of ethylenically unsaturated fatty acids having a chain of from 10 to 24 carbon atoms, wherein said adduct contains on an average at least 3 potentially reactive carboxy groups per molecule can be used to fulfill the objects of this invention. As explained in detail in commonly assigned application Ser. No. 264,069, filed Mar. 11, 1963, these methylol amides can be prepared by (l) reacting an adduct of an alpha, betaethylenically unsaturated dicarboxy compound (maleyl compound) and polyhydric alcohol ester with a basic nitrogen compound, which contains at least two active hydrogen atoms bonded to the same or diiferent nitrogen atoms in the same molecule, and (2) reacting the product of step 1 with a formaldehyde source.

In the description that follows, the Words dispersing and dispersion are used in a generic sense to be inclusive of the words suspending, dissolving, suspension and solution. The words ammonia and ammonium hydroxide are used interchangeably. The term formaldehyde is used in a generic sense to be inclusive of monomeric formaldehyde and formaldehyde-generating materials. The term potentially reactive carboxy group includes the following groups: the amide group, methylol amide group, the anhydride group, the carboxylic acid group and the carboxylic acid salt group.

The readily available naturally occurring glyceride oils,

such as soybean oil, corn oil, cottonseed oil, linseed oil, hempseed oil, tung oil, peanut oil, safflower oil, tobacco seed oil, cod oil, herring (or menhaden) oil, dehydrated castor oil, etc., are preferred because of their low cost and relatively large number of ethylenic double bonds available as sites for adduct formation. Other useful, though more expensive esters include linoleic acid esters of trimethylol propane, tall oil fatty acid esters of pentaerythritol, etc. In general, those compounds having on an average at least two and preferably three to nine nonconjugated ethylenically unsaturated groups per molecule are preferred. These can be thought of as being esters of a polyhydric alcohol (e.g., ethylene glycol, trimethylol ethane, glycerol, sorbitol, inositol, etc.) having from 2 to 6 hydroxyl groups with ethylenically unsaturated fatty acids of from 10 to 24 carbon atoms.

The maleyl compound (alpha, beta-ethylenically unsaturated dicarboxy compound) can be maleic anhydride, maleic acid, fumaric acid, dimethyl maleate, monomethyl hydrogen maleate, mono-Z-ethylhexyl hydrogen maleate,

citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride, ethyl maleic acid, maleimide, maleamicacid, etc. Of these, maleic anhydride is preferred because of (1) its low cost, (2) the ease with which it forms adducts in almost quantitative yields and (3) the high concentration of amide groups which result from the re-' action of the anhydride adduct with a basic nitrogen compound. While maleic acid, which forms the anhydride under the conditions of adduct formation has most of advantages of maleic anhydride, it is twice as expensive as the anhydride. Fumaric acid, which approaches the cost of maleic anhydride on a weight basis, requires considerably more severe reaction conditions to form an adduct and, even then, the yield is lower. Further,

adducts prepared from free dicarboxylic acids that are not cap-able of forming an anhydride under the conditions of the maleation reaction and from half-esters and diesters produce amides with a lower concentration of amide groups after treatment with a suitable basic nitrogen 7 form. It goes without saying that diesters are only suitable in this invention when at least some of the carboxy 3 groups in the diester adduct are saponified during or before the addition of the basic nitrogen compound to permit amide formation. Citric acid and malic acid which form alpha, beta-ethylenically unsaturated dicarboxy compounds under the conditions of the maleation reaction ca also be used in this invention. I

Ammonia, which can be employed as gaseous ammonia or in the aqueous ammonium hydroxide form, is the preferred basic nitrogen compound because of its low cost, availability, high vapor pressure in water, the ease with which it forms amides and the ease with which its amides form methylol groups. Various primary amines; such as methyl amine, ethyl amine, and butyl amine; primary and secondary polyamines; such as ethylene diamine, diethylene triamine, propylene diamine and N,N'-dimethylethylene diamine; can be used to partially or completely replace ammonia. All of these amines contain at least two active hydrogen atoms which may be bonded to the same or to different nitrogen atoms in the same molecule. Formaldehyde, generally as formalin, is the preferred source of formaldehyde. Polymeric forms of formaldehyde, such as trioxane and paraformaldehyde, are decidedly inferior to formaldehyde. These polymeric groups must be employed at much higher temperatures than the monomeric formaldehyde. Of course, the polymeric form is equivalent to the monomeric form if it is converted to the monomeric form before reaction with the amide adducts.

In somewhat greater detail the adduct is formed by reacting the long chain ethylenically unsaturated fatty com pound and the maleyl compound at a temperature of about 150" C. to 300 C. in an open vessel or under pressure in an autoclave. While maleic anhydride forms an adduct in almost quantitative yields in an open vessel, other maleyl compounds, such as dibutyl maleate, give considerably better yields when the reaction is carried out under pressure.

The ratio of maleyl compound to ethylenically unsaturated long chain fatty compound in the reaction vessel can range from about 0.2 to 2 moles or more of maleyl compound per equivalent of unsaturation in the long chain fatty ester depending upon the choice of reactants and the desired properties of the products. For example, the preferred naturally occurring glyceride oils, such as soybean oil or linseed oil, can be reacted with from about 15% to 45% by weight maleic anhydride to form adducts containing from about 1.5 to 4.5 maleic anhydride moieties per molecule of glyceride oil. (The resulting maleic anhydride portion of the glyceride oil adduct comprises from about 14% to 33% by weight of the product.)

The maleated long chain fatty material can be converted to the amide by a variety of techniques. For example, an anhydride adduct, such as that resulting from the maleation of a naturally occurring glyceride oil with maleic anhydride or maleic acid, can be converted to the amide form in any of the following ways: (1) stirring the anhydride adduct in an atmosphere of ammonia until the exothermic reaction ceases, (2) adding concentrated aqueous ammonium hydroxide (28% aqueous solution, for example,) to the anhydride adduct and stirring until the adduct disperses, (3) adding the anhydride adduct to concentrated aqueous ammonium hydroxide and stirring until the adduct disperses, (4) mixing the anhydride adduct with a calculated amount of water and then bubbling a suflicient amount of ammonia gas into the system to disperse the anhydride adduct, (5) mixing the anhydride adduct with a calculated amount of water, opening the anhydride ring by heating and then adding ammonia gas or aqueous ammonium hydroxide to disperse the adduct.

As explained in detail in application Ser. No. 264,069, the percentage of potentially reactive carboxy groups, which are converted to amide groups, can be readily controlled. The amine groups can typically comprise from about 7.5% to about 42.5% of the potentially reactive carboxy groups. In general, it is preferred that at least 4. one molecule of ammonia be added per each anhydride group (i.e. /2 mole of ammonia per each potential reactive carboxy group) in the adduct in order to prepare adducts, wherein at least 15% of the potentially reactive carboxy groups are amide groups.

The amide adduct, which has preferably been dispersed in water, is then reacted with formaldehyde or a compound capable of generating formaldehyde, preferably by adding the formaldehyde source (usually formalin or paraformaldehyde depolymerized to the monomeric form) to the amide adduct or by adding the amide adduct to the form aldehyde source. This reaction can be carried out in a sealed vessel at moderate temperature (5 C. to 75 C.) or in an open vessel. A sufiicient concentration of formaldehyde is added in this step to provide at least 0.2 mole (preferably at least 0.7 mole) of formaldehyde per each equivalent of nitrogen-containing compound bearing a nitrogen atom bonded directly to hydrogen (each NH group) in the aqueous composition. When 0.7 mole of formaldehyde or more is employed, the sizing composition can be advantageously cured to form a permanent, detergent-resistant, solvent-resistant coating, which cannot be removed from the woven fabric (of course, the size can be burnt off fiber glass fabrics).

After the formaldehyde reaction, the resultant methylol amide is neutralized or made basic by the addition of a suitable basic material such as alkali metal hydroxide (e.g. sodium hydroxide), ammonium hydroxide, a volatile amine, etc.

While the above described methylol amide can be employed as the sole component of the aqueous warp sizing bath in a concentration of about 1 to 60% active ingredient, best results, at the lowest cost, have been obtained by using the methylol amide in conjunction with a conventional hydroxyl-containing warp sizing agent, such as carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, and particularly starch.

In addition to the properties imparted to the hydroxylcontaining warp sizing agent, the methylol amide adduct acts as a preservative against the development of mold in starch pastes, such as a warp sizing baths, improves the clarity of the starch warp size on the sized yarn, and reduces theB.O.D. (biochemical oxygen demand) of the starch effluent from the alkaline desizing baths compared to the raw starch. Generally, aqueous starch warp sizing compositions of this type contain from about 2% to 25% by weight dry basis starch and from about 0.1% to 10% (preferably 0.3 to 4%) by weight methylol amide.

For the purposes of this invention, the term starch is used in a generic sense to include a naturally occurring starch, a modified starch, or a derivative of starch. Corn starch, tapioca starch, rice starch, potato starch, wheat starch, and the amylose and amylopectin fractions therefrom are representative of the various native starches and starch fractions that can be used. Any of these starches may be modified by enzyme treatment, by oxidation with hypochlorite or by heating with an acid or be derivatized by treatment with alkylene oxide, such as ethylene oxide or propylene oxide, partially esterified with an esterifying agent such as vinyl acetate or acetic anhydride. The starch derivatives also include carboxyrnethyl starch, carboxyethyl starch, N,N-diethylaminoethyl starch and other starch esters and ethers that can be used as sizing agents.

Apparently, the excellent adhesion and abrasion resistance of sized yarns (both of the hydrophilic and of the hydrophobic types) is due to the reaction of the methylol amide with the hydroxyl containing sizing agent. In gen eral, conventional warp sizing techniques (e.g. drying temperatures and time) are adequate to impart these properties while preserving the usually desired de-sizing char acteristics.

A permanent size can be imparted to the yarn by maintaining the methylol amide treated yarn at about C. for about 2 to 10 minutes. If a curing catalyst for the methylol amide, such as zinc ammonium acetate, zirconi- Example I A 12% slurry of unmodified corn starch (dry solids basis) was prepared. The starch was pasted in a high temperature steam-jet cooker, whose structure and operation are discussed in detail in application Ser. No. 790,487, filed Feb. 2, 1959, and now US. Pat. No. 3,101,284, using a 164 C. jet temperature, 98 p.s.i. jet steam pressure, 153 C. discharge temperature, 65 p.s.i. discharge pressure and one gallon per minute flow rate of starch slurry. Two parts by weight of a 60 percent active aqueous solution of a methylol amide having on an average 6 potentially reactive carboxy groups per molecule was added to the starch paste, (maintained at 93 C.) per each 100 parts by weight of starch paste (wet basis).

The 60% active aqueous solution of methylol amide was prepared in the following manner:

Eight hundred and eighty-four grams of bleached soybean oil (1 mole) was heated to 230 C. in a three-necked flask equipped with a stirrer, reflux condenser and addition port. After 294 grams (3 moles) of liquid maleic anhydride had been added through the addition port over a period of one and one-half hours, the composition was heated to 250 C. and held there for 15 minutes. The maleated oil, after cooling to about 50 C., was added to 700 grams of aqueous ammonium hydroxide (6 moles ammonia) and then the reactants were maintained at between 25-50 C., thereby dissolving the maleated oil. By distilling oil ammonia from a slightly basic sample of the solution, it was determined that about 42.5% of the potentially reactive carboxy groups (85% of the starting anhydride groups) had been converted to the amide form. Five hundred and fifteen grams of formalin (6.3 moles formaldehyde) were added rapidly to the solution and the pH of the aqueous system dropped to about to 5.5 precipitating the methylol amide as a water-insoluble hydrate. The water-insoluble hydrate was redissolved by slowly adding 143 grams of aqueous ammonium hydroxide (2.1 moles ammonia) while maintaining the exothermic reaction at about 50 C. The solution had a pH of about 7. Then 21.2 grams ethylene diamine (0.35 mole) and 52.0 grams aqueous ammonium hydroxide (0.77 mole ammonia) were added to adjust the pH of the aqueous solution of methylol amide to a value of 7.5- 8.5. The final product was approximately 60% active material.

The methylol amide-starch paste composition was used to size 30s cotton yarn on a model 51, Calloway slasher using a size box temperature of 93 to 95 C., squeeze roll pressure at roller arm #2 setting, speed at 36 yards per minute, first three dry cans at 121 C. and last dry can at 107 C.

The cotton yarn sized with the methylol amide-starch paste had an average abrasion resistance of 440 strokes on a Walker Abrader. In contrast, a control using only corn starch had an average abrasion resistance of 387 strokes. Further, the cotton yarn sized with the methylol amide-starch paste was transparent and there was no dificulty in identifying the color of the yarn. In the absence of the methylol amide the color of the yarn was masked. In addition, the starch paste containing the methylol amide was mold resistant.

6 Example 11 Example I was repeated using a hydroxyethyl corn starch having a D8. of between about 0.05 to 0.10 in place of the unmodified starch of Example I and the hydroxyethyl starch was pasted by cooking a 12% by weight starch slurry at 93 C.

The cotton yarn sized with the methylol amide-hydroxyethyl starch paste had an average abrasion resistance of 377 strokes on a Walker Abrader. In the absence of the methylol amide the cotton yarn sized only with the hydroxyethyl starch had an average abrasion resistance of 203 strokes.

Example III Example H was repeated using a low B.O.D. hydroxy ethyl corn starch having a D8. (degree of substitution) of about 0.4 in place of the low D.S. hydroxyethyl corn starch. The cotton yarn sized with the methylol amidehydroxyethyl starch had an average abrasion resistance of 580 strokes on a Walker Abrader.

Example V The glass fibers extruded from a 204 hole spinnerette were passed through a water mist, formed into a yarn, and sized by a kiss roll. The kiss roll sizing bath (60 C.) comprised 25 parts by weight of the 60% active methylol amide of Example I, 5 parts by weight of Carbowax 1540 lubricating agent and parts water. The warp size had excellent adhesion to the fiber glass yarn and gave the yarn an abrasion resistant finish.

Example VI A warp of Dacron (polyethylene terephthalate)-wool blend yarn was sized by the method of Example HI on a West Point Foundry Pacemaker except that the acidmodified corn starch-methylol amide composition used in Example III was employed at 16% total solids. The Warp size had excellent adhesion to the yarn and gave the yarn an abrasion resistant finish.

Example VII A terry cloth yarn was warp sized by the method of Example VI using an aqueous sizing bath containing 3% by weight of an acid-modified corn starch (D.S.B.) and 0.3% by weight of the 60% active methylol amide prepared in Example I. The sized yarn had excellent weaving properties and was readily desized in dilute alkaline desizing bath.

Since many embodiments of this invention can be made and since many changes maybe made in the embodiments described, the foregoing is to be interpreted as illustrative only and my invention is defined by the claims appended hereafter.

We claim:

1. A textile yarn carrying a dried size of a methylol amide of an adduct formed by reaction between a maleyl compound and an ester of an ethylenically unsaturated faty acid of from 10 to 24 carbon atoms with a polyhydric alcohol having from 2 to 6 hydroxyl groups, said adduct having on an average at least 3 potentially reactive carboxy groups per molecule.

2. The article of claim 1, wherein said maleyl compound comprises a compound selected from the group consisting of maleic acid and maleic anhydride.

3. The article of claim 1, wherein said dried size contains starch in a weight ratio of about 2 to 25 parts by weight starch per O.1 to parts by weight methylol amide. w 4. A textile yarn carrying a dried size comprising a methylol amide of a maleated ethylenically unsaturated glyceride oil having on an average at least3 potentially reactive carboxy groups per molecule.

5. A textile yarn carrying a sizing, wherein said sizingcomprises a product prepared by the steps of](1 react; ing a compound containing a basicnitrogen atom with an adduct of a maleyl compound and anester of an ethyl-l enically unsaturated fatty acid of from 10 to 24 carbon atoms with a polyhydric alcohol having from 2 to 6 by. droxy groups, the adduct having on an average at least 3 potentially reactive carboxy groups per molecule, and (2) reacting an aqueous solution of the reaction product of step (1) with formaldehyde.

6. The article of claim 5, wherein said maleyl compound comprises a compound selected from the group consisting of maleic anhydride and maleic acid; and said compound containing a basic nitrogen atom comprises ammonia.

7. The article of claim 6, wherein said ethylenicallyunsaturated fatty acid ester of a polyhydric alcohol comprises an ethylenically unsaturated glyceride oil.

' 8. The method of sizing textile yarns, which comprises passing the yarns through an aqueous sizing bath comprising a solution of a methylol amide of an adduct formed by reaction between a maleyl compound and an ester of an ethylenically unsaturated fatty acid of from 10 to 24 carbon atoms with a polyhydric alcohol having from 2 to 6 hydroxyl groups, said adduct having on an average at least 3 potentially reactive carboxy groups per molecule and drying said yarn.

- 9. The method of claim 8, wherein said maleyl compound comprises a compound selected from the group consisting of maleic acid and maleic anhydride.

I 10. The method of claim 8,'wherein said'sizing bath comprisesfrom 2.to 25% by weight pasted" starch and from about 0.1-to 10% by weight methylol amide.

.11. The method of sizing textile yarns, which comprises passing the yarns. through an. aqueous sizing bath comprising a solution of a methylol :amide' of a'male-' -'ate dj ethylenically, unsaturated glycer'ide 'o'il, wherein said methylol amide contains "on an' average at' least 3 p0- tentially reactive c'arboxy: groups per molecule'and drying' saidyarns. 1

12. A composition References Cited by the Examiner UNITED STATES PATENTS 2,188,885 1/1940 Clocker 260-404 XR 2,282,701 5/1942 Bock et al.

3,036,935 5/1962 Lolkema et al. 117-1395 3,101,330 8/1963 Paschall 106-210 ALEXANDER H. BRODMERKEL, Primary Examiner.

D. J. ARNOLD, Assistant Examiner.

' comprising 2 to 25, parts bywe'ight' starch and 0.1 to 10 parts by Weight methylol amide of 

12. A COMPOSITION COMPRISING 2 TO 25 PARTS BY WEIGHT STARCH AND 0.1 TO 10 PARTS BY WEIGHT METHYLOL AMIDE OF AN ADDUCT FORMED BETWEEN A MALEYL COMPOUND AND AN ESTER OF AN ETHYLENICALLY UNSATURATED FATTY ACID OF FROM 10 TO 24 CARBON ATOMS WITH A POLYHYDRIC ALCOHOL HAVING FROM 2 TO 6 HYDROXYL GROUPS, SAID ADDUCT HAVING ON AN AVERAGE AT LEAST 3 POTENTIALLY REACTIVE CARBOXY GROUPS PER MOLECULE. 